UNIT - 5

Polymerization
1. Olefin polymerization to yield polymer gasoline is primarily carried out to obtain
polymers with good octane numbers.

2. The octane number of the polymer gasoline product is not greater than the octane number
of the products produced from reforming and alkylation.

3. On the other hand, polymer gasoline has more vapour pressure than the corresponding
alkylation products.

4. Typical feedstocks for polymerization process are C3 and C4 olefins that are obtained
from catalytic cracking

5. The end product from polymerization reactor is a dimer or a trimer of the olefins.

AIM:
To produce polymer gasoline from C3 and C4 olefins

FEED:
Propylene and Butylene obtained from catalytic cracking unit

PRODUCT:
Polymer Gasoline

PRINCIPLE:
Polymerization (Dimer or Trimer polymerization – Oligomerization)
Polymerization – Smaller MW compound combined together to form higher
molecular weight compounds.

OPERATING CONDITIONS:

Temperature: 150 – 220 oC.

Pressure: 25 – 100 atms

Catalysts used: Acid catalysts (H2SO4).

REACTIONS:

olefin + olefin --> olefin

C=C-C + C=C-C --> C-C-C-C=C-C

C=C-C-C + C=C-C --> C-C-C-C-C=C-C

MAJOR EQUIPMENT INVOLVED:

1. Polymerization Reactor
2. Fractionator
3. Caustic wash tank

FLOW SHEET:

PROCESS DESCRIPTION:
Caustic wash: C3-C4 olefin feed subjected to caustic wash to remove H2S and other sulphur
compounds (such as mercaptans). These tend to poison the catalyst.
Water scrubbing: Eventually water scrubbing is carried out to remove dissolved impurities
and generate waste water.
Polymerization reactor: The reaction mixture is heated, compressed and fed to a
polymerization reactor. The reactor design is a shell and tube type design where catalyst is
placed in the tube for the reaction to take place and cooling water is circulated in the shell
side to control the temperature increase due to the exothermic reaction.
Fractionation: Subsequently, the reactor product is fed to a depropanizer and debutanizer to
produce propanes, butanes and polymer gasoline. The polymeric product is further
stabilization using hydrogenation stabilizer which converts any freely available double bonds
to single bonds. The end product is polymer gasoline
The propane produced is partially recycled to the reactor and the other part taken out as a
product.

REACTION MECHANISM:

Reaction mechanism comprises of four basic steps

Step 1:
Carbonium ion formation: Here, olefin reacts with acid catalyst to yield carbonium ion.

Step 2:
Additon reaction: Carbonium ion reacts with olefin to generate intermediate carbonium ion

Step 3:
Regeneration: The intermediate carbonium ion converts to the dimer and generates back the
proton on the catalyst surface
TYPICAL YIELD:

Feed:

Propane - 22 wt%

Butane - 36 wt%

C3 & C4 Olefins - 42 wt%

Product yield:

Product composition:
Product Quality:
GREASE
 Grease is a solid-to-semifluid mixture of a fluid lubricant, a thickener, and additives.
It also defined as, Grease is a solid-to-semifluid product of dispersion of a thickening agent
and additives in a liquid lubricant.

Composition of Grease:

Greases are made of three components: thickeners, oils and additives. Thickeners are
ways to gel the grease and typically range from 3%-30% of a grease by volume. Oils in
greases are the key components that allow them to act as lubricating fluids and typically
compose 70%-95%. Additives impart or enhance specific performance aspects to the
lubrication and can range from 1%-10% of grease’s volume.

• Lubricating oils and additives are the major constituents in a grease formulation. Additives
enhance performance and protect the grease and lubricated surfaces.

A liquid lubricant must have the following basic functions:

• Create a film between moving parts to minimize friction and wear
• Act as a coolant by heat removal

As a pure lubricant, however, grease does have many advantages over fluid oil. A grease can
be said to have four major 'abilities': lubricating ability, sealing ability, corrosion inhibition
ability and carrying (matrix) ability, all pertaining to a material's consistency and multi-phase
structure.
BASE OIL:
The fluid lubricant that performs the actual lubrication can be petroleum (mineral) oil,
synthetic oil, or vegetable oil.

• Majority of greases on the market are composed of mineral oil blended with a soap
thickener.

Bright base oil (150 stock) is lubricant oil has been used as base oil for grease production in
Iraqi refineries. It is paraffinic oil, produced from vacuum distillation residue after removal of
asphalt. Table 1 shows some of base oil’s properties:

ADDITIVES:
1. Enhance existing desirable properties
2. Suppress existing undesirable properties
3. Impart new properties
4. Use small amounts of grease for longer time frames under higher operating
temperatures
Antioxidants
• Extend the life of the lubricant by inhibiting oxidation
• Minimize base oil thickening, sludging and deposits
• Eg. sulphur additives such as polysulfide’s and sulphurized isobutylene

Scavengers
• React with undesirable contaminants such as acids or Sulphur to render them less harmful

Anti-wear agents
• inhibit wear under high-speed and low load operating conditions
• E.g.. polymers or solid additives

Corrosion Inhibitors
• inhibit the corrosion of metals in contact with the lubricant.
• E.g. dialkysithiophosphate which is based on long chained alcohols.

Extreme Pressure (EP) Agents

• inhibit seizure under high loads and temperatures.
• E.g. disulphide and graphite

Friction Modifiers
• Reduce the friction between moving parts by surface adsorption
• E.g. organic molybdenum complexes and derivatives of long chain fatty acids

Metal Deactivators
• Inhibit the metals contacting the lubricant from catalyzing oxidation of the lubricant.
• E.g. Aromatic triazole

Seal Swell Agents

• Assist elastomer seals and gaskets to perform their function
• E.g. Dibasic ester

FUNCTION OF GREASE:

1. The function of grease is to remain in contact with and lubricate moving surfaces
without leaking out under gravity or centrifugal action.

2. Grease should retain its properties under shear at all temperatures that it is subjected
to during use.

3. Grease must be able to flow into the bearing through grease guns to all parts of the
lubricated machinery as needed, but must not add significantly to power requirements.

CHARACTERISTICS OF GREASE:

Common ASTM tests for grease characteristics include:

  Apparent viscosity
 Bleeding, migration, syneresis
 Consistency, penetration, and National
 Lubricating Grease Institute (NLGI) numbers
 Corrosion and rust resistance
 Dropping point
 Fretting wear and false brinelling
 Oxidation stability
 Pumpability and slumpability
 Shear stability
 High and low temperature effects

WHEN SHOULD A GREASE BE USED?

Oil cannot be confined

1. Relubrication is difficult or dangerous

2. Noise reduction is important
3. It is required to reduce time spent lubricating
4. For equipment used intermittently
5. For extreme conditions of:
- High temperature
- High pressure
- Shock loads
- Low speed combined with high loads

ADVANTAGES OF GREASE LUBRICATION

Better stop-start performance – when the system shuts down, oil drains away while grease
remains in the component

Contamination – the risk of contamination products such as food and pharmaceutical type
products is reduced with the use of grease due to its resistance to flow into the products
• Greases decrease dripping, splattering and leakage
• Greases reduce noise
• Greased machinery tends to need less power
DISADVANTAGES OF GREASE LUBRICATION

Reduced cooling/heating transfer – the flow of oil removes heat from the point of
generation where it can be removed or dissipate. Grease tends to hold heat in place

Poorer storage ability – too long storage can lead to separation of base oil and thickener and
may also result in altered properties
• Greases may not reach all places in need of lubrication
• Greases cannot be used at the high speeds that liquids are well suited for

SIX CATEGORIES OF GREASE

1. Mineral Oil Mixed With Solids

2. Heavy Asphaltic-Type Oil Blends
3. Roll Neck Greases
4. Soap Thickened Mineral Oils
5. Multipurpose Greases

1. Mineral Oil Mixed With Solids

Heavy lubricants
 Heavy pressure loads at slow speeds
 Concrete mixers, bearings, rollers

2. Heavy Asphaltic-Type Oil Blends

Blended with lighter oils
 Chemical reaction forms a film to prevent metal-tometal contact
 Contains additives to improve film strength
  Additives depend on equipment load, speed, surface condition and inherent design
characteristics

3. Roll Neck Greases

Plain bearings in rolling equipment
 Consistency of a bar of soap
 Heavily loaded equipment

4. Soap Thickened Mineral Oils

Most widely used in industry
 Sodium-base grease
 Barium-soap grease
 Lithium-soap grease
 Calcium-soap grease

5. Multipurpose Grease
Combined properties of two or more greases
 Reduced number of greases required
 Multi-component application
 High melting point, water resistant and
 exceptional Stability

GREASE PRODUCTION PROCESSES:

Grease manufacturing process classified in to two types based on operating mode:

1. Batch Process
 Lower costs,
 Able to meet varying demand,
 process variables can be subjected to adjustment

2. Continuous Process
 Reduced cycle time,
 improved process control

Grease manufacturing process classified in to two types based on Types of grease:

 Soap-based (eg. Calcium, Lithium)
 Non soap based (eg. polyurea and clay thickeners)
Production of Calcium based Grease

Aim: Production of Calcium based Grease from lubricating base oil

Feed: i) Base Oil

needed

ii) Thickener
Ca(OH)2, LiOH is most widely used

iii) Additives
Eg. Corrosion inhibitors, friction modifiers

Product: Calcium based grease

Reaction:

Equipment Involved:

a. Kettle
b. Agitation-blend reaction products
c. Introduction of additives and lube oil inputs
d. Dehydration-Removal of water by-product
e. Heating/cooling jackets
f. Temperature control
g. Homogeniser/Miller
h. Milling: break agglomerated particles
i. De-aeration, filtering: adjust the grease consistency, smooth and stable product

Block diagram for the production of Calcium-Base-Grease

Flow-Chart-Lithium-Base-Greace

FACTORS AFFECTING GREASE QUALITY

a. Temperature of grease formation

 b. Rate of cooling of reaction products
c. Rate / Sequence of addition of oil and additives
d. Rate of saponification reaction
e. Acidity / Alkalinity
f. Temperature of additive addition
g. Temperature and duration of de-aeration, filtrations and
h. Homogenization

IMPORTANT TEST FOR GREASE:

1. Grease Consistency

The most important test for grease is the ASTM D217 Grease Consistency Test that
ensures the grease has a consistent starting point. A weighted cone is dropped into level
grease and the depth of penetration is measured: the greater the depth, the softer the grease.
The penetration is measured after 60, 10,000 and 100,000 double strokes. A change in
consistency gives an indication of application stability.

2. Droping Point:

The next most important test is the Dropping Point Test, specified by ASTM. This
tests
the temperature at which the thickener matrix can no longer hold oil, which is the point when
the grease can no longer serve its purpose. The dropping point temperature is not the melting
point of the grease. The higher the dropping point temperature, the better. A thin smear of a
small sample the size of a thimble is watched to see when droppable oil falls from a cup as
the temperature is increased. According to the ASTM method, grease is tested up to a
maximum of 316 C (600 F).

3. Ball WearTest and the 4-Ball EP Test.

Greases also are tested for wear and load performance with the 4-Ball Wear Test and
the 4-Ball EP Test. The wear test identifies wear and boundary wear regimes. One ball is
rotated under load against three stationary balls held tight in a metal cup filled with the test
grease.
The test is run at 40 kg, 1200 rpm and 75 C for 60 minutes. The diameters of the circular
scars formed on the three lower balls are measured in millimeters and averaged. The smaller
the diameter the better protection afforded.

The 4-Ball EP Test pushes and goes beyond the wear regime. One ball is again rotated
under load against three stationary balls held tight in a metal cup filled with the test grease.
Run at 1770 rpm, 25 C for 10 seconds, this test starts at 80 kg and adds successive loads to
800 kg or until welding occurs. The weld point is reported. The Load Wear Index is a
measure of the wear associated during the testing. The higher the number the better the
lubricant can protect against wear at high loads.

4. Water washout test

In the ASTM D1264 Water Washout Test, grease is weighed before and after one
hour of testing to see how much of it has been removed from a shielded packed bearing with
a water
spray impinging on it. A motor spins a bearing and pumps water running at 600 rpm, with a 5
cm3/s flow rate and either 79 C or 38 C water. The bearing is dried in an oven, and the
weight loss after one hour is determined.

5. Spray tests.
In the ASTM D4049 Water Spray Resistance Test, a weighed amount of grease is
coated on a horizontal metal panel and is exposed directly to water spray from above for five
minutes
(see Figure 9). The panel is dried in an oven and the weight loss is used to determine the
percent sprayed off. The less removed the better.
 PETROLEUM JELLY

What’s the difference between petroleum jelly and Vaseline?

Vaseline is the original, name brand for petroleum jelly. Theoretically, there is no difference
between the name brand and generic brands. However, Unilever, the company that makes
Vaseline, claims that they only use the highest quality ingredients and a special purification
and filtration process. There may be small variations in consistency, smoothness, or even
fragrance with Vaseline and generic brands. However, there does not appear to be a
difference in safety between products. The best advice is to read the label. It should be simply
100 percent petroleum jelly.

What is petroleum jelly made of?

Petroleum jelly (also called petrolatum) is a mixture of mineral oils and waxes, which form a
semisolid jelly-like substance. This product hasn’t changed much since Robert Augustus
Chesebrough discovered it in 1859. Chesebrough noticed that oil workers would use a gooey
jelly to heal their wounds and burns. He eventually packaged this jelly as Vaseline.
Petroleum jelly’s benefits come from its main ingredient petroleum, which helps seal your
skin with a water-protective barrier. This helps your skin heal and retain moisture. Read on to
learn what else you can use petroleum jelly for.

Benefits and uses for petroleum jelly

1. Heal minor skin scrapes and burns

A study showsTrusted Source that petroleum jelly is effective in keeping skin moist during
post-surgery healing. This may be particularly good for regular, less dramatic skin injuries.
Make sure that the surface you apply petroleum jelly on is properly cleaned and disinfected.
Otherwise, bacteria and other pathogens can get trapped inside and delay the healing process.

2. Moisturize your face, hands, and more

Face and body lotion: Apply petroleum jelly after a shower. As an occlusive moisturizer, it
prevents your skin from drying out. You can also use it for dry noses during cold or allergy
season.

Cracked heels: Soak your feet in warm water with some salt added to it. Towel-dry
thoroughly and apply petroleum jelly and clean cotton socks.

Improve your gardening hands: After washing and drying, use some petroleum jelly and a
clean pair of gloves to help lock in moisture and accelerate healing.

Chapped lips: Apply to chapped lips as you would any chapstick.

3. Help for pet paws

Your dog’s pad skin can crack and produce a great deal of discomfort. Clean their paws with
cotton gauze, dry, and apply the jelly. Ideally this should be done after a walk or when your
pet is resting.
Read more: Choosing a healthy facial moisturizer »

4. Prevent diaper rash

Petroleum jelly has been shownTrusted Source to reduce the incidence of diaper rash in
babies. Clean and towel-dry your little one’s skin properly before applying. Petroleum jelly
will form a protective barrier that will help protect the skin from constant exposure to
moisture. Make an appointment with the doctor if there is a persistent rash.

5. Remove eye makeup

Oil is an effective way to remove makeup, and petroleum jelly is safe to use in the eye area,
according to a study on eye ultrasounds. Use a cotton pad or Q-tip (for hard to reach areas),
and press gently without tugging too hard on your skin. Make sure to close your eyes as you
wipe. Some people also swear by using it on crow’s feet lines.

6. Save split ends

Sun and wind exposure as well as pool water can dry up your hair. Petroleum jelly can reduce
the look of split ends and add shine to your hair. Rub a small amount of jelly between your
palms and apply to hair ends.

7. Prevent skin stains from hair dye or nail polish

Apply petroleum jelly along your hairline to prevent hair dye from staining your skin. This
also works if you like to paint your nails at home. A barrier of petroleum jelly is easy to wipe
away when you’re done.

8. Preserve perfume scents

Using petroleum jelly as a base for your perfume can help it last longer.
9. Use as lube for stuck objects

If a ring is stuck on your finger, put some jelly on your finger, making sure you get some
around and under the ring. This will help the ring slip off your finger.

For door hinges, apply a bit of jelly right on the hinge and swing the door a few times to
spread evenly. Wipe off the excess.

Dangers of petroleum jelly

While petroleum jelly has many benefits, it should be for external use only. Do not eat or
insert petroleum jelly. Avoid using petroleum jelly for masturbation or as a vaginal lubricant.
According to Reuters, a study of 141 women found that 17 percent used petroleum jelly
internally and 40 percent of them tested positive for bacterial vaginosis.

The brand and type of jelly you purchase may cause different reactions. These include:

Potential side effects

 Allergies: Some people are more sensitive and can develop allergies if they use
petroleum-derived products. Always keep an eye out for irritations and adverse
reactions when using a new product.

 Infections: Not allowing the skin to dry or cleaning the skin properly before applying
petroleum jelly can cause fungal or bacterial infections. A contaminated jar can also
spread bacteria if you insert jelly vaginally.

 Aspiration risks: Check with your doctor before using petroleum jelly around the nose
area, especially in children. Inhaling mineral oils may cause aspiration pneumonia.

 Clogged pores: Some people may break out when using petroleum jelly. Make sure
you clean the skin properly before you apply the jelly to reduce the risk of breakouts.
Petroleum jelly vs. Vaseline

Q:

What’s the difference between petroleum jelly and Vaseline?

A:

Vaseline is the original, name brand for petroleum jelly. Theoretically, there is no difference
between the name brand and generic brands. However, Unilever, the company that makes
Vaseline, claims that they only use the highest quality ingredients and a special purification
and filtration process. There may be small variations in consistency, smoothness, or even
fragrance with Vaseline and generic brands. However, there does not appear to be a
difference in safety between products. The best advice is to read the label. It should be simply
100 percent petroleum jelly.

The bottom line

Petroleum jelly has been a staple in the medical and beauty industry for a long time due to its
emollient properties, ability to help with skin healing, and also due to its safe record. Be sure
to choose triple-distilled, purified product (the well-known old timer Vaseline is one of them)
in order to avoid putting any toxic contaminants on your skin, some of which are potentially
carcinogenic.